Zn 催化剂对次烟煤及其镜质组富集物催化解聚影响
ZnCl2 catalyst on the catalytic depolymerization of sub bituminous coal and its vitrinite rich concentrate
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摘要: 选用一种次烟煤为研究对象,利用格金干馏实验装置、全二维气相色谱-质谱联用仪 (GC×GC-MS)、气相色谱仪,通过考察添加不同含量的 ZnCl2 催化剂对催化解聚产物分布、焦油组 成、气体组成及半焦的影响,探讨添加 ZnCl2 催化剂及催化剂添加量对原煤催化解聚反应的影响规 律和可能作用机制。 催化解聚产物分布结果表明,添加 Zn 基催化剂可促进煤热反应程度,降低半 焦产率,提高焦油产率。 Zn 添加量为 0.10%时对煤热反应过程的促进程度最高,焦油产率增加也 最高,从原煤的 12.05%增加至 13.83%,其焦油组分分析表明,焦油中多环芳烃类物质的相对含量 增加幅度最大。 结合气体组分分析,气相中 H2 体积分数增加明显,而 CH4 体积分数略有降低,C2+ 等低碳烃类气体明显减少,CO,CO2 体积分数基本不变,表明在 Zn 基催化剂作用下,较小自由基更 倾向于与一些大自由基碎片结合生成大分子焦油,而不是小分子气体。 在此基础上,考察了 0.10% Zn 基催化剂添加对原煤提质分离所得的镜质组富集煤样的催化解聚效果,结果表明,原煤提质可 显著提升焦油产率,镜质组富集煤样焦油产率达到 16.17%,较原煤增加了 4.12%,且 Zn 基催化剂 添加可进一步提升镜质组富集煤样热解聚程度,进一步提升焦油产率至 17.87%。Abstract: The effects of adding different contents of ZnCl 2 catalysts into sub bituminous coal on the catalytic depolymerization products of tar composition,gas phase composition and char were investigated by Gray King assay,gas chromatography analysis,and comprehensive two dimensional gas chromatography mass spectrometry (GC×GC MS) and its possible catalytic mechanism was discussed. The product distribution results showed that after the addition of the ZnCl 2 catalyst,the yield of char was reduced and the yield of tar was improved. When the addition amount of Zn was 0.10%,the promotion effect on the pyrolysis catalytic depolymerization was the highest,the tar yield increased to 13.83% compared with 12.05% of the raw coal. According to the results of tar components analysis,the content of polycyclic aromatic hydrocarbons in the tar increased the most. Gas phase composition analysis showed that the H 2 content increased significantly,while the CH 4 content decreased slightly,the C 2+ and other low carbon hydrocarbons decreased significantly,and the CO and CO 2 yields remained basically unchanged. It indicates that with the addition of the Zn based catalyst,free radicals were more inclined to generate large molecular tar with some large free radical fragments,rather than small molecular gases. Moreover,the catalytic depolymerization effect of the addition of 0.10% Zn based catalyst on the vitrinite rich concentrate obtained from the separation of the sub bituminous coal was investigated. The tar yield obtained from the depolymerization of the vitrinite rich concentrate reached 16.17%,which was an increase of 4.12% compared to the raw coal. Also the Zn catalyst addition could further increase the thermal depolymerization degree of vitrinite rich concentrate and further increase the tar yield to 17.87%.